Aroylene-bis-acetic acid-arylides



UNITED STATES "PATENT" OFFICE AnornsNa-nrseaosrro Aom AnYLmEs- Franz Henle and Herbert Kracker, Frankforton-the-MaLin-Hochst; Germany, assignors' to General Aniline Works, Inc., New acorporation ofDelaware" York, N. n,

No Drawing. Application Januaryfi, 1 933,,Serial No. 650,588. In Germ any September 9, 1930 6 Claims.

The present, invention relates to aroylene-bis: acetic acid-arylides, more particularly it relates to compounds of the following general formula:

zene naphthalene-or diphenyl-seriess r This application is a continuation-in-part application to our copending application Serial No.

591,444, filed February 6, 1932. i

We have found that the hitherto unknown aroylene-bis-acetic acid-arylides (wherein the term aroylene means the radical CO-RCO- of an aromatic dicarboxylic acidlmay be obtained,

for instance, by condensing the aroylene-bisacetic acid-esters (obtainable by condensation of aromatic dicarboxylic acid chlorides withacetoacetic acid-esters, according to the statements in Journal fiir .praktische Qhemie, vol. 74, pages 124to 126, and subsequent acid cleavage) with aromatic amines, for instance, according to the statements in Annalen denChemie, vol. 2515,; page 372, relating to the preparation of: benzoyl v acetic acid-anilide or according to the statements in British Patent No. 16928 of 1912, relating to the manufacture of; (i-substitution products of.

aceto-acetic acid anilide and its homologues,

The new compounds are distinguished by a high ailinity tor the vegetable fiberand are "valu able intermediates" for the production of a20- dyestuffs.

The followingle iamples serve to illustrate the; invention, but they are not intended tolimit it'f thereto, the parts beingbyweighti (1) 306 parts of terephthaloylrbis acetic acidethyl ester obtainable, .for instance, according to the statements "in. fqournal fiir praktische Chemie,"vol. 74, page's'12'4 to 126), and 186 parts of aniline; are heated in an oil-bath. Vivid reactionsetslin between 135 C. and .140 C. and

which is at first clear, and the mass becomes more and more viscous. 'Whenthe frothing has ceased,

the reaction mixture has solidifiedto a brittle,

after filtration, the hot solution is acidified by means of hydrochloric acid. There isobtained the terephthaloyl-bis-acetic acid-anilide in the form of a yellowish crystalline powder which melts at 230 C. to 231 C. i Q

It corresponds to the formula:

(2) 306 parts of terephthaloyl-bis-aceticfacidethyl-ester, 3'76 parts of .1-amino-3-chloro-'4.6- dimethoxybenzene and 1500 parts of Xylene are heated to boiling. The ethyl-alcohol, formed during the reaction, is distilled oil, thesolution is allowed to cool and the terephthaloyl-bis-acetic acid-Bwhloro;efi-dimethoxy-l-anilide which has separated in the form of crystals is filtered by suction. It forms in the dry state a yellow crystalline powder which melts at 268 C. to 269 C. The compound dissolves to a. light-yellow solution in' organic solvents and in aqueous caustic alkalies. Instead of xylene, th re may be used any other, high-boiling; indifferent solvent, as, for instance, toluene, chlorobenzene, solvent naphtha, nitrobenzene and others. Instead of terephthaloyl bis acetic acid-ester, there niay, be used any. homologue; as, for instance, chloroterephthaloyl-bis-acetic acid-ester, naphthoylene-bis-acetic acid-ester, biphenyl 4.4-dicarbonyl-bisacetic acid-ester or the like which may be obtained, for instance, in a manner analogous to, the preparation of terephthaloyl bis acetic acid-ester according to the statements in Journalfiir' praktische Chemie, vol. 74, pages 124 to 126 by starting from the corresponding aromatic dicarboxylic acid chloride and aceto-acetic acid-ester."

Instead of 1 amino-3-chloror4.6-dimethoXybenzene, there may be used any other base. Thus,

s, R stands for a radical of the benzene-, naphthaleneor diphenyl series, being crystal- Terephthaloyl -bisacetic acid-ester and o-chloroaniline Terephthaloyl-bis-aceticacid-o-chloroanilide Yellow crystals, melting at 208 C. to 209 0. p-anisidine- Terephthaloyl-bis-acetic acid-p-anisidide Yellow crystals, melting at 242 C. to 243 C. o-toluidine Terephthaloyl-bis-acetlc acid-o-toluidide Feebly yellowish crystals, melting at 225 0., to 226 C. a-naphthylamine- Terephthaloyl-bis-acetic acid-a-naphthylami e1. Yellow crystals, melting at 257 C. to 258 C. B-naphthylamine. Terephthaloyl-bis-acetic acid-B-naphthylamide. Yellow crystals, melting at 250 C. to 251 C. 2.5-dichlorc ani- Terephthaloyl-bis-acetic acid-2.5-dichloroanilide. White needles, melting at 239 0. to 240 0.,

line. a 1-amin0-2-meth- Terephthaloyl-bis-actic acid-2-methyl-4-ehloro-1-anilide Feebly yellowish small crystals, melting at 273 0. to

yl 4 chloro 2 274 (3., r benzene. l-amino-2-metl1- Terephthaloyl-bis-acetlc acid-Z-methoxy-E-chloro-1-aml1de Yellowlsh crystals, melting at 252 C. to 253 0.,0

oxy 5 chlorobenzene. r m-nitraniline Terephthaloyl-bis-acetic acid-m-nrtranil1de Dark yellow crystals, melting at 249 C. to 250 C p-toluidine Terephthaloyl-bis-acetic aeid-p-toluidi de Yellowish crystals, melting at 244 0. to 245 C. l-aminoclll Terephthaloyl-bis-acetic-acid-4-chloro-2.-5-dimethoxy- -an1- Dark yellow crystals, melting at 267 C. to 268 C 2.5 dimethoxylide. benzene. 1-amino-2-meth- Terephthaloyl-bis-acetlc acid-2-methoXy-4-chloro-l-aml1de Yellow crystals, meltnig at 249 C. to 250 C.

oxy 4 chlorobenzene. 1-amino-4-chloro-2- Terephthaloyl-bis-acetie acidi-chloro-2-methoxy5-meth Light-yellow crystals, melting at 265 C. to 260 0.

methoxy 5 yl-l-anilide. methylbenzene. I t p-aminodiphenyl- Terephthaloyl-bis-acetmacid=p=ammodiphenyl. :Yellow crystalline powder, melting at above 310 C.

Isophthaloyl bis acetic acid-ester and Aniline Y e em oroaniline- 'I'sophthaloyl-bis-acetic acid-o-chloroanilide Isdphtlialoyl bis-acetic acid-anilido Pale-yellow crystals, meltingat186 C. to 187 Pale-yellow crystals, melting at 152 C. to'

Blphenyl 4;4"-dicarbonyl bis acetic acid-ester "land Aniline 1-amino-4-cl1lor0- 2 -metlioxybenzene.

Dark yellow crystals, melting at 235 C; to 236 C. Dark yellow crystals, melting at 237 C.

N itro terephthal oyl bis acetic acid-ester and o-toluidine o-anisidine.

Yellow crystals, melting at 272 Yellow crystals, melting at 264 Ohloro terephthal oyl r-rbis acetic acid-ester and 1 amino-2-methoxy 4 chlorobenzene. l-a'minoi-chloro- 2.5-dimthoxy benzene.

Chloro-terephthaloyl-bis-aoetic acid-2-methoxy-4-chloro-1- anilide.

Chloro-terephthaloyl-bis-acetic 'acid-i-chloro-Zfi-dimetb oxy-l-anillde.

Light-yellow crystals, melting at 276 C. to 277 C.

Naphthoylene 1.5- bis-acetic acid ester and Aniline Naphthoylene-l.5-bis-acetic acid-anilide;

Naplitlioylene-l..B-bis-acetic'acid-o chlorwanilide Y Yellow crystals, melting at 296 ellow crystals, melting at 308 We claim; I I

1. The compounds of the following general formula:

R',-NHCOCH2CO-R wherein R and R. stand for radicals of the benz'ene-, naphthaleneor diphe'nyl seri'es, being crystallized yellow eompounds soluble in organic solvents and in aqueous alkali with a yellow color and being'distinguished by a high' affinity for the vegetablefiber.

2. The compounds of the following general formula:

wherein R stands forv a radical ofthe benzene lized yellow compounds soluble in organic solvents and in aqueous alkali with a yellow color and being distinguished by a high affinity for the vegetable fiber.

3. The compounds of the following general formula? Y wherein R and R stand for radicals of therb en zene series, being crystallized yellow compounds, soluble in organic solvents and in aqueous alkali OCH;

representing a yellow crystalline powder which melts at 268 C. to 269 C. and being distinguished by a. high afiinity for the vegetable fiber.

6. The terephthaloyl-bis-acetic acid--chloro- 2-methoxy-5-methyl-l-a,nilide of the following formula:

OCH; OCH;

representing a light yellow crystalline powder which melts at 265 C. to 266 C. and being distinguished by a high affinity for the vegetable fiber.

FRANZ HENLE. HERBERT KRACKER. 

